Conversion of solid fuels and products derived therefrom or other materials into valuable liquids



Aug. 22, 1933.. c KRAUCH 5 AL 1323 573 CONVERSION OF SOLID FUELS ANDPRODUCTS DERIVED THEREFROM OR OTHER MATERIALS INTO VALUABLE LIQUIDSOriginal Filed Feb. 6, 1926 fiea'clio'n plamler Purzlf 2' 719 System J!Fm! w 3 5 wage me Car] Kmzicl Mullins-Pier INVENTORS ATTORNEYS PatentedAug. 22,

CONVERSION OF SOLID FUELS PROD- 'UCTS DERIVED THEE FROM OR OTHERMATERIALS INTO VAL ABLE LIQUIDS cm Kraucb, Ludwigshafen-on-the-Rhine,and Mathias Pier, Heidelberg, Germany, assignors, by mesne assignments,to Standard-I. G. Company, Linden, N. J-.,

ware

a Corporation of Dela- Original application February 6, 1926, Serial No.86,646, and in Germany- February 14, 1925. Divided and this applicationApril 7, 1927.

Serial No. 181,885

26 Claims.

One of the most important and widely agitated problems in the industrialworld has for a long time been how to produce good gasoline or othervaluable liquid fuels from distillable carbonaceous materials such assolid fuel including coal in all its varieties and wood, and products ofdistillation or mineral oils especially heavy oils.

One attempt at the solution of this problem has been made bytheso-called liquefaction of coals by means of hydrogen or bydestructive hydrogenation of tars or oils under a high pressure at hightemperature but this has not reached application industrially because ofan unsatisfactory speed and rate of the conversion.

=By the process described in the specification of the originalapplication No. 86,646 filed Feb- In arriving at this result we havemade several discoveries or inventions to certain of which thisapplication is directed.

We conceived the idea of applying a catalyst to the said solid fuel orother materials, in connection with said hydrogenizing high pressure andhigh temperature process, but found that an improvement of the processcould not be obtained at all or at least not in a continued operation.Thereafter we discovered that the 'cause of this drawback was the sulfurpresent in the treated material and we found that combinewsulfur is' avery suitable catalytic substance immune to sulfur poisoning.

Such combined sulfur may be'added in diilerent forms, for example ofsulfides, single or mixed, also in mixture with metals, metalloids oroxids, hydroxids, or carbonates and the like, es-

pecially in mixture with catalysts promoting hydrogenation. Sulfids ofheavy metals, particularly those of the iron group, whether alone or inmixtures, are of special efllclency. Sulfur may also be introduced inother forms, for example by adding sulfites or sulfates, or adding freesulfur to metals or metal oxids and the like and thereby generating acontact mass containing combined sulfur. Also by treating iron withsulfuretted hydrogen at an elevated temperature a contact mass oflasting efficiency can be produced.

The said catalysts may be added in .any suitable manner. 'materials theymay be placed in the reaction 'vessel and theliquids brought intocontact with them in a vaporizedor otherwise finely divided state. Whenoperating with solid carbonaceous materials the catalysts may besupplied to them by grinding both these materials and the catalysts andmixing the ground masses. Other bodies, for example, lumps of brick,quartz, asbestos, coke, active carbon, silica 'gel, metals, especiallyheavy metals, or metal oxids, or carbids, or mixtures of such bodies,may also be present in the reactiofi chamber. These additional bodieshave a dispersing action accompanied in some cases,

In the case of working with liquid as'for example in the case of activecarbon, silica tars or oils obtained by pressure hydrogenation of solidor liquid fuels, or components or conversion products of all abovementioned materials, such as cracked products, cumarone or any otherresins or residues of their distillation, pitch,

asphaltum and soon, or mixtures of several such products witheach-other, also of solids with liquids or of one or more of suchproducts with other suitable organic liquids.

Especially'when employing coal or liquid fuels, an addition of ligniteor peat is often of advantage, often increasing the hydrogenizingaction, avoiding several drawbacks and in the case of solid substances.rendering their introduction easier. v

All the said materials may be used in the presence of substantialamounts of water' and, if .desired, water may be added as such.Sometimes the process of hydrogenation is hereby furthered. For example,lie ite producer tar containing from 40 to 50 per cent of water may beused to advantage directly.

The preferred form of carrying out the process is generally a continuousoperation with a stream of the gases and with an excess thereof over therequired quantity and preferably while maintaining the desired pressureby adding fresh gas and passing the gas either by circulation throughone or more reaction vessels or through a succession of several reactionvessels. The material to be converted is supplied at a proper place andthe products are separated from the reaction gases by cooling. r

The gases serving for the reaction may consist of hydrogen alone or ofmixtures containing hydrogen, for example a mixture of hydrogen withnitrogen, or water gas, or hydrogen mixed with carbon dioxid, hydrogensulphide, water vapor or methane or other hydrocarbons. Or the hydrogenmay be generated in the reaction chamber by the interaction of waterand, carbon production obtained by the process is very large.

* hydrogenation treatment .of solid fuels, cars,

mineral oils and other materials referred to, which compounds may becomprised by the term destructively hydrogenized fuels are generallyvery low in sulfuroreven completely free therefrom and are excellentlysuitable for use ,as'fuel for internal combustion engines.

In the accompanying drawing an apparatus for carrying out theprocessaccording to the present invention is illustrated diagrammatically,partly in vertical section.

Referring to the drawing in detail reference numeral 1 indicates a feedline from any convenient source of liquid raw material. The line 1discharges to a grinding mechanism 2 fitted with a hopper 3 throughwhich solid materials may be admitted. If desired, the grindingmechanism can be by-passed by line la when no solid materials are used.The suspension of solid material in liquid or the liquid alone may bethen forced by pump 5 through a line 4 to a heat exchanger 6 and thenceby line '7 into a reaction chamber 8. The reaction chamber isconstructed in any preferred manner and should be adapted to withstandhigh pressures, for example, 20, 100 or even ashigh as 1000 atmospheres,as well as the corrosive effects of the reactants. The .vessel ispreferably protected from loss of heat by a suitable insulating cover 9and may be heated ,by electric coils 10 which are arranged within thedrum. The contents of the drum are preferably kept in a state ofagitation by means of a stirring mechanism 11 and the catalyticmaterials 11' as indicated above may be attached to the stirringmechanism so that the catalyst is brought into intimate contact with thecontents of the vessel.

Hydrogen under high pressure is forced through a line 12, heat exchanger13 and then by line 14 into the base of the reactor.8 into which it ispreferably discharged through a spray pipe 15. A liquid level may bemaintained in the drum, for example at the point 16a and gas andvaporous products may be continuously withdrawn by vapor line 16 whichis in communication with exchanger 13 and a cooling coil or condenser17. The condensate and gas is discharged into a separating drum 18 fromwhich the distillate is removed by line 19 to storage, not shown. Thegas may be taken off by a pipe 20 to a purifying system indicated at 21,and which may comprise a scrubbing system preferably carried out at highpressure using, for example, soda to remove hydrogen sulfide and oil toremove hydrocarbon constituents from the gas. The hydrogen sulphide, andthe hydrocarbon constituents are removed from the gas in order toprevent their becoming too concentrated in the hydrogenating gas which,after some time, would lower the partial pressure of hydrogen to anundesirable extent and also, particularly due to the hydrogen sulphide,give riseto increasing attack on the constructional materials of thehydrogenating vessels. Purified gas is then recompressed by a boosterpump 22 and isforced again into the hydrogen feed line 12. Freshhydrogen may be introduced by line 23. If desired, oil may becontinuously removed from the drum by a line 24 which communicates withheat exchanger 6 and which is withdrawn to storage, not shown, by asuitable line 25.

be in the neighborhod of .3 to -.8 volumes of oil per hour per volume ofreaction space. vaporous materials may be treated at higher temperatureslikewise vary considerably and should always, of

course, be in excess of that actually required for the conversion; forexample, the rate of flow of hydrogen may be in excess of about 600litres per kilogram of carbonaceous material.

The following examples will serve to further explain how our inventionis carried out in practice, but we do not restrict our invention tothese examples. 7

' Example 1 From 30 to 60 grams per hour of raw cresylic acid obtainedfrom coal tar are passed together with from 300 to 600 liters ofhydrogen under a pressure of 150 atmospheres and at a temperature-offrom 380 degrees to 400 degrees centigrade over from 30 to 50 cubiccentimeters of a contact mass obtained by pressing precipitated cobaltsulfid into lumps. The reaction sets in 7 per cent of silicon, 0.27 percent of manganese,

carbons.

tion products thereof into valuable liquids of difvividly after a shortwhile and proceeds ata constant velocity. In the product obtained bycool-..

ing, the phenols are largely reduced to hydrobrown coal tar or rawdistillates thereof, phenolic bodies contained therein-are reduced tohydrocarbons to a satisfactory degree notwithstanding the presence ofhydrocarbons and impurities,

and iron, or by zinc sulfid, or aluminium sulfid,

or other contact masses containingcombined sulfur.

Example 2 2.5 kilograms per hour of dark-colored residues of an Americanrock oil, which at ordinary temperature are nearly solid and have astrongly unsaturated character, are passed continuously together with6000 liters of hydrogen under a pressure of 200 atmospheres and at from450 degrees to 500 degrees centigrade over 3000 cubic centimeters of acontact mass prepared by forming precipitated cobalt sulfid. Alight-colored, mobile liquid is produced besides a little methane, whichon distillation yields 50 per centof a fraction up to 150 degrees andadditional 35 per cent up to 350 degrees centigrade, all of a saturatedcharacter. The small residues are viscous or Vaseline-like and free ofpitch. H In all of the above examples the hot parts of the apparatus maybe lined or coated with aluminium or aluminium alloys or chromium ormade of or coated withan alloy of per cent of nickel, 27.7 per cent ofiron, 12 per cent of chromium and 0.3 per cent of carbon; or an alloycomposed of 58 per cent of nickel, 25 per cent of iron, 17 per cent ofchromium and 0.3 per cent of carbon; or an alloy composed of 96 per centof iron, 1.75 percent of nickel, 1.5 per cent of chromium, 0.1 per centof carbon and'also of 0.25

besides small quantities of copper, sulfur and phosphorus.

Our invention is notconfined to the above examples; the conditions maybe widely varied. in various directions. For example the pressures andtemperatures may be higher or lower than stated above.

In the appended claims, the expression distillation and extractionproducts thereof is intended to relate only to solid and liquiddistillation and extraction products and is'not' to be construed toinclude normally gaseous products of the distillation of solid andliquid fuels.

Also, when the catalyst set forthin the claims isdefined as being added,it is not to be construed, as necessarily meaning that the catalyst isintroduced into the reaction chamber with each charge of carbonaceousmaterial, but is to be construed to mean that the reaction is carriedout in the presence of an effective quantity of a catalytic materialwhich is not naturally contained Similarly, when treating coal tar or.

may be re-' placed by a mixture of the sulfids of cobalt and a nickel,orof cobalt and manganese, or of cobalt ferent molecular weight whichcomprises treating them with hydrogen in the presence of an added solidwcatalyst containing a polyvalent metal and sulphur at a temperaturesufficient to promote the conversion, and under a jpressureof at least20 atmospheres. g '2. The process of destructively hydrogenizingdistillable carbonaceous substances of the nature of solid and liquid.fuels, distillation and extraction products thereof into valuableliquids of difierent molecular weight which, comprises treating themwith hydrogen in the presence of an added solid catalyst containing aheavy metal and sulphur at a temperature sufficientto promote ;.theconversion and under afpressure of at least 20 atmospheres.

3. The process of destructively hydrogenizing distillable carbonaceoussubstances'of the nature of solid and liquid fuels, 'distillationfandextraction products therecfinto valuable liquids of different molecularweight which comprises treating them with hydrogen in.,the presence ofan added polyvalent metal sulphide at a temperature suflicient topromote the conversion, and under a pressure of at least: 20atmospheres.

4.,The process of destructively hydrogenizing distillable carbonaceoussubstances of the. nature of solid and liquid fuels, distillation andextraction products thereof into valuable liquids of different molecular.weight which comprises treating them with hydrogen in the presence ofan added heavy metal sulphide ata temperature sufiicient to promote theconversion, and under a pressure of at least 20 atmospheres.

5.- The process of destructively .hydrogenizing distillable carbonaceoussubstances of the nature of solid and liquid fuels, distillation andextraction products thereof into valuable liquids of different molecularweight which comprises treating them with hydrogen in the presenceof anadded solid catalyst containing a metalof the iron group and sulphur ata temperature sufficient to promote the conversion and undera pressureof at least 20-atmospheres.

6. The process of destructively hydrogenizing distillable carbonaceoussubstances of the nature of solid and liquid fuels, distillation andextraction products thereof into valuable liquids of different molecularweight which comprises treating them with hydrogen in the presence of anadded sulphide of a metal of the iron group at a temperature suiiicientto promote the conversion, and under a pressure of at least 20atmospheres.

'7. The process of destructively hydrogenizing distillable carbonaceoussubstances including naturally occurring solid and liquid fuels,distillation and extraction products thereof, into valuableliquids'substantially free from asphaltum, which comprises charging agas containing hydrogen with vapors of said substances and exposing themixture to a pressure of at least 20 atmospheres and to heatat atemperature Sllfilcient to promote conversion in the presence of anadded solid catalyst containing a polyvalent metal and sulphur, theinitial material and the hydrogen being continuously supplied to'and theproduct and the hydrogen being continuously removed from the reactionchamber.

8. The process of destructively hydrogenizing distillable carbonaceoussubstances including naturally occurring solid and liquid fuels,distillation and extraction products thereof, into f valuable; ,liqu'idsshamans nee from is.

phaltumfiwhich comprises charging a gas conoff100 atmospheres and toheat at a temperature sufficient to promote conversion in the presenceof an added solid catalyst containing 'a heavy metal and-sulphur andremoving the product from the reaction chamber in admixture with thestream of escaping hydrogen.

9.'The process of'destructively hydrogenizing distillable carbonaceoussubstances including naturally oocuring solid and liquid fuels,distillation and extraction products thereof, into valuable liquidssubstantially free from asphaltum, which comprises charging a 'gascontaining hydrogen with vapors of. the said substances and exposing themixture to a pressure of at least 20 atmospheres and to heat at atemperature sufficient to promote conversion in the presence of an addedpolyvalent metal sulfid, removing the product from the reactionchamberin admixture with the stream of escaping hydrogen, separating thereaction product from the hydrogen and returning the hydrogen to thereaction-zone. 0

10. The process of destructively hydrogenizing distillable carbonaceoussubstances of the nature of solid and liquid fuels, distillation andextraction products thereof into valuable liquids of different molecularweight which comprises charging a gas containing hydrogen with vapors ofsaid substances and exposing the mixture to the action of an added heavymetal sulphide at a temperature sufficient to promote the conversion andunder a pressure of .at least 20 atmospheres.

11. The process of destructively hydrogenizing distillable carbonaceoussubstances including naturally occurring solid and liquid fuels,distillation and extraction products thereof, into valuable liquidssubstantially free from asphaltum, which comprises charging a gascontaining hydrogen with vapors of said substances and exposing themixture to a pressure upwards of 100 atmospheres and to heat at atemperature sufli cient to promote conversion in the presence of anadded heavy metal sulfid, removing the product from the reaction chamberas a vapor in the stream'of escaping hydrogen; cooling the mixed steamin order to condense the hydrocarbon vapors and separating the hydrogenfrom the con-.

densate.

12. The process of destructively hydrogenizing distillable carbonaceoussubstances including naturally occurring solid and liquidfuels,distillation and extraction products thereof, into valuable liquidssubstantially free from asphaltum, which comprises charging a gascontaining hydrogen with vapors of said substances and exposing themixture of a pressure of at least 20 atmospheres and to heat at atemperature sumcient to promote conversion in the presence of an addedsulfid of a metal of the iron group, removing the product from thereaction chamber asa vapor in the stream of escaping hydrogen, coolingthe mixed stream in order to condense the hydrocarbon vapors, separatingthe uncondensed hydrocarbons at least in part from the hydrogen, andrecycling the hydrogen through the reaction vessel.

13. The process of. destructively hydrogeniz'ing Y distillablecarbonaceous substances of the nature of solid and liquid fuels,distillation and extraction products thereof which comprises treatingthem with hydrogen in the presence of an added catalyst immune to svtvhur poisoning comprising essenat a temperature suflicient to promoteconversion means tially, a metal sulphide at a temperature between 300and 700 C., andat a pressure ranging 1111-.v

' wards of 100atmospheres.

14.'The process of converting distillable carbonaceous substances such"as solid and liquid fuels,- distillation and extraction productsthereof, into valuable liquids, which comprises treating them with addedhydrogen in the presence of an added solid catalyst containing apolyvalent metal and sulphur, at a temperature of between about 300 and700 C. and at a pressure of at least 20 atmospheres. I

p 15. The process of converting carbonaceous substances such as solidand liquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises treating them with added hydrogen inthe presence of an added solid catalyst containing a heavy metal andsulphur, at a temperature 'of-between about 300 and 700 C. and at apressure of at least 20 atmospheres.

16. The process of converting carbonaceous substances such as solid andliquid fuels, distillation and extraction products thereof, intovaluable liquids which comprisestreating them with added hydrogen in thepresence of an added heavy metal sulfid, at a temperature of betweenabout 300 and 700 C. and at a pressure of at least 20 atmospheres.

17. The process of converting carbonaceous su stances such as solid andliquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises treating them with a stream ofhydrogen in the presence of an added heavy metal sulfid, at atemperature .of between about 300 and 700 C. and at a pressure upwards11 of 100 atmospheres.

' 18. The process of converting carbonaceous substances such as solidand liquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises treating them with added hydrogen inthe presence of an added sulfid of a metal of the iron group, at atemperature of between about 300 and 700 C. and at a pressure upwards of100 atmospheres.

fuel I materials, which comprises destructively hydrogenizing theinitial material with added hydrogen in the presence of an added heavymetal sulfid, at a pressure of at least 20 atmospheres and at atemperature of between about 300 and 20. The process of convertingliquid carbonaceous substances into lighter hydrocarbons, whichcomprises destructively hydrogenizing the initial material with addedhydrogen in the presence of an added heavy metal sulfid, at a pressureof at least 20 atmospheres and at a temperature of between about 300 and700 C.

21. The process of destructively hydrogenizing distillable carbonaceoussubstances including naturally occurring solid and liquid fuels,distillation and extraction products thereof, intovaluable liquids whichcomprises treating them with hydrogen in the presence of cobalt sulfidand heat 0 and at a pressure of at least 2.0 atmospheres. 3

22. The process of destructively hydrogenizing distillable carbonaceoussubstances including naturally'occurring solid andfliquid-fuels,distilla- 1 tion and extraction products thereof, into valuable liquids,which comprises treating them with a stream of hydrogen in the presenceof cobalt sulfid and heat at a-temperature sufficient to promoteconversion and at an elevated pressure of at least 20 atmospheres.

24. The process of converting carbonaceous substances such as solid andliquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises treating them with added hydrogen inthe presence of added cobalt sulfid, at a temperature of between about300 and 700 C. and at a pressure of at least 20 atmospheres,

25. The process of converting'carbonaceous substances such as solidand'liquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises treating them with added hydrogen inthe presence of zinc sulfid, at a temperature of between about 300 and700 C. and at a pressure of at least 20 atmospheres.

26. The process of converting carbonaceous substances such as solid andliquid fuels, distillation and extraction products thereof, intovaluable liquids, which comprises treating them with added hydrogeninthe presence of manganese sulfid, at a temperature of between about 300and 700 C. and at a pressure of at least 20 atmospheres. 1 r

CARL KRAUCH. MATHIAS PIER.

